Saturday, June 27, 2009

INTERCALATION COMPOUNDS, BATTERIES, AND PATENTS:WHAT HAPPENS AFTER GRAD SCHOOL

I. Graphite/Chromium trioxide

A. Background

Our first publication showed that grahite/chromium trioxide prepared by the Croft method was NOT an intercalation compound of graphite but rather a physical mixture of graphite and Cr3O8. X-ray diffraction was definitive on the point, but other lines of proof appeared in the paper. Ten years elapsed without much commentary on the point, until a certain worker in Poland claimed there was an intercalation compound prepared by the Croft method. Various papers appeared at this point.

B. Science issue

Inability of reviewers to understand the significance of a Cu K-beta peak in x-ray radiation in a diffraction experiment performed with filters rather than a monochromator.

At Stanford, second moment calculations on the F-19 NMR absorption of CF were used to show carbon monofuoride had a boat conformaton, rather than the previously reported chair conformation and the results were published in J. Am.Chem Soc. Although the second moment was calculated using double integration techniques, a later paper, (appearing after I left Stanford) also published in J.Am.Chem.Soc, suggested our result was wrong, because we used only single integration. I (naively) thought it would be an easy matter to correct the factually incorrect assertion about the single integration.

But no, J. Am. Chem. Soc. had an editorial policy not allowing third party commentary on published articles, and as to the second J.Am.Chem.Soc paper, I was a third party. J.Am.Chem.Soc. would not allow correction of an error about what the Stanford work did. Years went by, but I finally had a chance to state the issue, and correct the misstatement in the second J.Am.Chem.Soc. article, curiously in a symposium proceedings of a symposium I did not attend.[3] But the story did not end there.

I was appointed to the “Ethics Task Force” of the American Chemical Society, where I had a chance to bring up the issue of journals issuing corrections. As a lawyer, I participated in a litigation wherein an uncorrected error in J.Am.Chem.Soc. produced a multi-million dollar patent case. [4] Nevertheless, even with this example, the ACS (and JACS) would not alter the policy. Mistakes last forever. Legal publications suffer the same problem. [5]

B. Science issue

The inability of a journal to correct a mistake in a published paper leads to later workers overlooking key issues, here the large second moment of the F-19 NMR absorption, which cannot be reconciled with the chair model.

In my own experience, I came across one episode which illustrated the inability of the scientific community to deal with each side of the coin. In a paper by D. L. Wertz and M. Bissell, Energy & Fuels, 1994, 8, 613-617 on the diffraction of the graphene layer ["(002)"] peak in bituminous coals, the authors stated that the diffraction peak was "far too intense to be caused by amorphous scattering and far too broad to be caused by conventional diffraction." The authors cited three papers to justify this assertion. Of three papers relied upon to prove the statement, which was the key assumption in the paper, one was non-existent, one was irrelevant and one supported a contrary position. Following use ofthe key assumption, the authors utilized an undefined short range interference function to manipulate the x-ray diffraction data of the paper. The modified data led to a remarkable conclusion: that analysis of a peak related to interference between aromatic entities (sp2 hybridized carbon) could predict the amount of aliphatic carbon (sp3 hybridized carbon). Pertinent prior work on diffraction of "poorly crystalline" carbonaceous systems with sp2 and sp3 carbon was ignored.

I contacted the editor of the journal. Of the non-citation and mis-citation issues, nothing was done, and in fact the mis-citation was repeated in a later paper.

The Journal of the American Chemical Society has a policy of not allowing mistake correction by third parties, and the present author has direct experience with this policy. This author wrote a paper on the calculation of the second moment of the fluorine nuclear magnetic resonance (NMR) of solid poly (carbon monofluoride), which led to the conclusion that the structure contained an infinite array of cyclohexane boats, rather than the expected chairs, J. Am. Chem. Soc., 1974, 96, 7841, which boat structure was reproduced in the Cotton and Wilkinson, 4th edition. Five years later, different workers, who also published in JACS, criticized the calculation, on the basis that it involved a single integration, rather than a double integration. Although the allegation had no basis in the text of the 1974 paper, and was untrue, the journal (which did not dispute the truth of what this author said) would not allow a comment to be published. Five years later, this author did publish a comment, which appeared in the Proceedings of the Workshop on Electrochemistry of Carbon, pp. 595-607, Electrochemical Society Proceedings Series, Volume 84 No. 5 (1984). (Poly(carbon monofluoride) is a useful cathode for high energy density lithium batteries.)

Thomas R. Krawietz and James F. Haw, Characterization of poly(carbon monofluoride) by 19F and 19F to 13C cross polarization MAS NMR spectroscopy, Chem. Commun., 1998 2151 [One such study concluded that (CFx)n is an arrayof cis-trans-linked boats, with all fluorine in axial positions. Amore recent student used similar methods to support a transtrans-linked chair structure, and that conclusion is supported bythe available X-ray data. (…)samples of (CF0.87)nand (CF1.12)n The mostintense peak in both spectra, at 187 ppm, is assigned bycomparison to the fluorines on C9 and C10 of either trans- orcis-perfluorodecalin, each at 186 ppm. Therefore, the 187ppm resonance in Fig. 1 is confidently assigned to C–Fgroups.]

Medical Power, LLC, a leading supplier of batteries for implantable medical devices, today announced the introduction of its enhanced Lithium Carbon Monofluoride (Li/CFx) battery technology with end-of-life capability superior to currently available products in the market. The technology includes a proprietary new Elective Replacement Indicator (ERI) / End of Life (EOL) Indicator to accurately predict battery depletion six months in advance, potentially requiring fewer replacement surgeries over time.

III. The problem of ignoring the literature

A. Background

In parts I. and II., examples were given wherein there was an engaged debate of relevant science issues, although the dialog was imperfect, either through the inability of reviewers to recognize basic science facts or through the unwillingness of scientific editors to correct errors.

A different pathology arises when authors/reviewers/editors simply choose to ignore relevant published papers.

B. Science issues

When authors/reviewers/editors ignore relevant published papers, great waste occurs.

The correct quinoid structure for the dimer of triphenylmethyl radicals was proposed in 1904. By 1906 there existed three independent lines of evidence which support this structure: acid-catalyzed aromatization, para-halogen lability, and radical chain autoxidation. Despite this evidence, and the skill and insight of the numerous chemists who studied the system,the incorrect hexaphenylethane structure was assigned to the dimer until 1968. This paper attempts to explain how this could have happened by tracing the evolution of triphenylmethyl theory and of attitudes toward the evidence from 1900 until 1968.

Hot off the press: the paper by Cecil D. Quillen, Jr. and Ogden H. Webster, Continuing Patent Applications and Performance of the U.S. Patent and Trademark Oﬃce—One More Time, The Federal Circuit Bar Journal, 379 (2009)

which begins: This Article is the fourth by the authors reporting the eﬀect of continuing patent applications on performance of the United States Patent and Trademark Oﬃce (“USPTO”) and updates our earlier studies through the USPTO’s 2008 ﬁscal year (“FY”) and through 2007 for the European and Japanese Patent Oﬃces (“EPO” and “JPO,” respectively).1

manages not to cite the variety of papers criticizing the first three papers in the series.

In recent proposals for patent reform made by the Federal Trade Commission and by the National Academy of Sciences, there has been discussion of the possibility that the grant rate of patents by the United States Patent and Trademark Office [USPTO] is high compared to that of other industrialized countries, including that of Japan and those of Europe. This discussion began with papers of Quillen and Webster that suggested that the grant rate might be as high as 97% and more reasonably is at least 85%. Although the actual grant rate at the USPTO is typically in the range 62% to 68%, Quillen and Webster suggested the higher numbers based on an analysis of continuing applications (including continuations, divisionals, and continuations-in-part). The present paper suggests that the analysis of Quillen and Webster is flawed both legally and methodologically, and that recent work by Clarke, which places the corrected grant rate at less than 75%, is more accurate.

AND

The need to be "up to date" in Shepardizing cases is well recognized within the legal community.14 In the present situation pertaining to patent grant rates, the impact of the first paper by Quillen and Webster, which asserted a 97% patent grant rate, extended later in time than the second paper by Quillen and Webster which withdrew the 97% patent grant rate and posited (among other numbers) an 85% patent grant rate. Thus, the Harvard Law Review15and the chief patent counsel of Intel16 referred to the conclusions of the first Quillen and Webster paper in the year 2003, after the conclusions had been modified in 2002.17

AND

The patent grant rate studies of Quillen and Webster are flawed and the published grant rate numbers should not be relied upon in making arguments about patent reform. The models of Quillen and Webster erroneously assume that all continuing applications are repeated attempts to patent the invention of the parent application. The methodology of Quillen and Webster, even as modified in 2002, involves double counting of patents and artificially inflates the patent grant rate. The approximations of Clarke are more reliable than those of Quillen and Webster.

While Quillen and Webster based grant rate on applications "allowed," Clarke based his studies on applications "issued." In this paper, we use data from the USPTO to show that the difference between "allowed" and "issued" applications is not the reason for the divergence in grant rates. Instead, we suggest that Quillen and Webster's elevated grant rates arise from a flawed numerical approach.

AND

John R. Allison and Emerson H. Tiller, The Business Method Patent Myth, 18 Berkeley Tech. L.J. 987, at footnote 139 of QWII: "adjusting assumptions from previous study to correct a probable flaw, but still producing an estimated allowance rate much higher than reported, and higher than in Japan and Germany."

AND

In a different area, in the context of the plagiarism issue involving Professor Laurence Tribe of Harvard Law School,20 Professor Allan Dershowitz suggested there was a “cultural difference” between sourcing in the legal profession and other academic disciplines.21 One would hope that there is no cultural between law and other academic disciplines as to the correction of published text which is indisputably wrong.22

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About Me

I'm a patent lawyer located in central New Jersey. I have a J.D. from the University of Chicago and a Ph.D. from Stanford University, where I studied graphite intercalation compounds at the Center for Materials Research. I worked at Exxon Corporate Research in areas ranging from engine deposits through coal and petroleum to fullerenes. An article that I wrote in The Trademark Reporter, 1994, 84, 379-407 on color trademarks was cited by Supreme Court in Qualitex v. Jacobson, 514 US 159 (1995) and the methodology was adopted
in the Capri case in N.D. Ill. An article that I wrote on DNA profiling was cited by the Colorado Supreme Court (Shreck case) and a Florida appellate court (Brim case). I was interviewed by NHK-TV about the Jan-Hendrik Schon affair. I am developing ipABC, an entity that combines rigorous IP analytics with study of business models, to optimize utilization of intellectual property. I can be reached at C8AsF5 at yahoo.com.